US8323532B2 - Positive electrode material formed by a lamellar-type oxide for a lithium battery - Google Patents

Positive electrode material formed by a lamellar-type oxide for a lithium battery Download PDF

Info

Publication number
US8323532B2
US8323532B2 US12/996,510 US99651009A US8323532B2 US 8323532 B2 US8323532 B2 US 8323532B2 US 99651009 A US99651009 A US 99651009A US 8323532 B2 US8323532 B2 US 8323532B2
Authority
US
United States
Prior art keywords
group
mno
positive electrode
lamellar
chemical element
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active, expires
Application number
US12/996,510
Other languages
English (en)
Other versions
US20110089369A1 (en
Inventor
Sébastien Patoux
Carole Bourbon
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Original Assignee
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Commissariat a lEnergie Atomique et aux Energies Alternatives CEA filed Critical Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Assigned to COMMISSARIAT A L'ENERGIE ATOMIQUE ET AUX ENERGIES ALTERNATIVES reassignment COMMISSARIAT A L'ENERGIE ATOMIQUE ET AUX ENERGIES ALTERNATIVES ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BOURBON, CAROLE, PATOUX, SEBASTIEN
Publication of US20110089369A1 publication Critical patent/US20110089369A1/en
Application granted granted Critical
Publication of US8323532B2 publication Critical patent/US8323532B2/en
Active legal-status Critical Current
Adjusted expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/125—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3
    • C01G45/1257—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type[MnO3]n-, e.g. Li2MnO3, Li2[MxMn1-xO3], (La,Sr)MnO3 containing lithium, e.g. Li2MnO3, Li2[MxMn1-xO3
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/20—Two-dimensional structures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to a lamellar-type oxide, in particular used as active material of a positive electrode for a lithium battery and to a method for synthesizing such an oxide.
  • Lithium batteries are progressively replacing nickel-cadmium (Ni—Cd) or metallic nickel-hydride (Ni-MH) batteries as autonomous power source, in particular in portable equipment. This tendency can be explained by the continuous improvement of the performances of lithium batteries giving them substantially higher mass and volume energy densities than those of Ni—Cd and Ni-MH batteries.
  • the first Li-ion type lithium batteries had a mass energy density of about 85 Wh/kg, a mass energy density of about 200 Wh/kg can be obtained at present.
  • Ni—MH batteries and Ni—Cd batteries respectively have a mass energy density of 100 Wh/kg and 50 Wh/kg.
  • lithium batteries have to be further improved. Improving the performances of Li-Ion batteries and in particular increasing their capacity are closely related to the search for new active electrode materials.
  • the active materials generally used for negative electrodes in commercial lithium batteries are carbon (graphite, coke, . . . ), a spinel oxide of Li 4 Ti 5 O 12 type or a metal forming an alloy with lithium such as Sn or Si.
  • the active materials used for positive electrodes in commercial lithium batteries are compounds of lamellar-type structure, such as LiCoO 2 and LiNiO 2 oxides, or compounds of spine structure such as LiMn 2 O 4 and derivatives thereof.
  • these compounds have to be further improved and the electrode/electrolyte interface has to be stabilized at high voltage as the lifetime is about a few tens of cycles and is therefore low.
  • These compounds furthermore have low theoretical specific capacities generally comprised between 145 and 170 mAh/g.
  • Another possible path for improvement consists in finding active materials for the positive electrodes of lithium batteries having higher specific capacities than the active materials used at present.
  • Lamellar-type oxides of LiMO 2 type, where M represents a transition element such as cobalt, do however enable theoretical capacities that are among the highest to be obtained.
  • the theoretical capacities are in fact comprised between about 270 to 300 mAh/g, according to the molar mass of the transition element. In practice however, the capacity obtained is generally about 150 mAh/g, due to the obligation of preserving the structural coherence of such oxides.
  • LiNi 0.8 Co 0.15 Al 0.05 O 2 and LiNi 1/3 Co 1/3 Mn 1/3 O 2 compounds also of lamellar-type structure, enable similar or substantially higher electrochemical performances to be obtained than oxides of LiMO 2 type for lower or equal cost and an improved chemical stability in particular in charged state.
  • oxides of xLi 2 M′O 3 .(1 ⁇ x)LiMO 2 type where:
  • Such oxides have the particularity of presenting multiple electrochemical phenomena associated with the changes of oxidation degrees of the different transition elements. This enables high specific capacities to be obtained in certain cases, paving the way for development of particularly attractive active materials. However, it is not sure that the specific capacity can be maintained with such materials when cycling takes place. A decrease of the specific capacity can in fact be observed in the course of the charging/discharging cycles. A great deal of progress therefore still remains to be made in order to propose active materials for positive electrodes enabling a high and stabilized specific capacity to be obtained, therefore providing Lithium-Ion batteries with improved performances.
  • the object of the invention is to propose active materials for the positive electrode remedying the shortcomings of materials according to the prior art and in particular, in the field of lithium batteries, enabling a stabilized in cycling and high specific capacity to be obtained, advantageously at all the cycling temperatures usually used and in the usual range of potentials.
  • this object is achieved by a new family of lamellar-type oxides of following general formula: x Li 2 MnO 3 .(1 ⁇ x )LiM 1 a M 2 b M 3 c O 2
  • the lamellar-type oxide is represented by the following formula: 0.75Li 2 MnO 3 .0.25LiNi 0.9 Mn 0.05 Mg 0.05 O 2 .
  • FIG. 1 represents the variation of the specific capacity on discharge versus the number of cycles, in intentiostatic mode (C/10 conditions, 55° C.), of Lithium batteries comprising lithium as active material for the negative electrode and respectively 0.75Li 2 MnO 3 .0.25LiNiO 2 , 0.75Li 2 MnO 3 .0.25LiNi 0.6 Mg 0.2 Mn 0.2 O 2 and 0.7Li 2 MnO 3 .0.3LiMn 1/3 Ni 1/3 Co 1/3 O 2 as active material for the positive electrode.
  • FIG. 2 represents an X-ray diffraction diagram ( ⁇ cuK ⁇ ) of the compound of formula 0.75Li 2 MnO 3 .0.25LiNi 0.9 Mn 0.05 Mg 0.05 O 2 prepared according to a first particular embodiment.
  • FIG. 3 corresponds to a scanning electron microscopy image of the compound of formula 0.75Li 2 MnO 3 .0.25LiNi 0.9 Mn 0.05 Mg 0.05 O 2 prepared according to a first particular embodiment.
  • FIG. 4 represents the variation of the specific capacity on discharge versus the number of cycles of a lithium battery comprising the compound 0.75Li 2 MnO 3 .0.25LiNi 0.9 Mn 0.05 Mg 0.05 O 2 as active material for the positive electrode, during testing performed in intentiostatic mode under C/10 conditions with a temperature of 55° C., between 3 and 4.8 V vs. Li + /Li.
  • FIG. 5 represents the charging/discharging curve plot (potential versus specific capacity) at the hundredth cycle of a lithium battery comprising the compound 0.75Li 2 MnO 3 .0.25LiNi 0.9 Mn 0.05 Mg 0.05 O 2 as active positive electrode material, when testing is performed in intentiostatic mode between 2.5 and 4.8 V vs. Li + /Li, under C/10 conditions at a temperature of 55° C.
  • FIGS. 6 and 7 represent the curve plot of the first discharge (potential versus specific capacity) of a lithium battery comprising a compound 0.75Li 2 MnO 3 .0.25LiNi 0.9 Mn 0.05 Mg 0.05 O 2 obtained according to an alternative embodiment and used as active positive electrode material, when testing is performed in intentiostatic mode between 2.5 and 4.8 V vs. Li + /Li, under C/10 conditions respectively at a temperature of 55° C. and 20° C.
  • FIG. 8 represents the variation of the specific capacity on discharge versus the number of cycles (C/10 conditions) of lithium batteries the first discharge of which is plotted in FIGS. 6 and 7 .
  • Lamellar-type oxides of the following general formula: x Li 2 MnO 3 .(1 ⁇ x )LiM 1 a M 2 b M 3 c O 2 (1) where:
  • oxides of the general formula (1) comprise at least one electrochemically inactive chemical element (M 3 ), also called chemical element devoid of electrochemical activity.
  • electrochemically inactive chemical element is a chemical element that does not oxidize or that is not reduced during charging or discharging of a lithium battery, in the usual range of potentials.
  • M 3 is more particularly at least a chemical element chosen from the group formed by Mg, Zn, Al, Na, Ca, Li, K, Sc, B, C, Si, P and S. M 3 can thus also be formed by several of the chemical elements of the above-mentioned group. M 3 thereby enables the specific capacity on cycling to be indirectly stabilized.
  • M 3 is further associated:
  • M 1 is nickel
  • M 2 is manganese
  • M 3 is magnesium
  • b is moreover preferably equal to c.
  • the positive electrode of a lithium battery can thus comprise a majority quantity of an oxide of the general formula (1) as active material.
  • the positive electrode advantageously comprises minority quantities of an organic binder such as a polyether, a polyester, a polymer with a base of methyl methacrylate, acrylonitrile, or vinylidene fluoride and an electron-conducting additive such carbon.
  • the lithium battery also comprises a negative electrode the active material of which can be of any known type.
  • the active material of the negative electrode can be lithium in metal form or it can be a material able to insert and de-insert Li + ions, such as carbon in general in graphite form, an oxide such as Li 4 Ti 5 O 12 or a compound forming an alloy with lithium such as silicon or tin.
  • the electrolyte of the lithium battery in general comprises a lithium salt for example chosen from LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiR F SO 3 , LiCH 3 SO 3 , LiN(R F SO 2 ) 2 , LiC(R F SO 2 ) 3 , lithium bis(trifluoromethanesulphonyl)imide (also noted LiT F SI), lithium bis(oxalato)borate (also noted LiBOB), lithium bis(perfluoroethylsulfonyl)imide (also noted LiBETI), or lithium fluoroalkylphosphate (LiFAP).
  • a lithium salt for example chosen from LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiR F SO 3 , LiCH 3 SO 3 , LiN(R F SO 2 ) 2 , LiC(R F SO 2 ) 3 , lithium bis(trifluoromethanesulphonyl
  • R F is a radical chosen from a fluorine atom and a perfluoroalkyl group containing between one and eight carbon atoms.
  • the lithium salt is further preferably dissolved in an aprotic polar solvent.
  • the salt is for example supported by a separating element arranged between the two electrodes of the battery, the separating element then being imbibed with electrolyte.
  • the lithium salt is not dissolved in an organic solvent, but in a solid polymer composite such as polyethylene oxide (PEO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride (PVdF), polyvinyl chloride (PVC) or a derivative thereof.
  • a solid polymer composite such as polyethylene oxide (PEO), poly(acrylonitrile) (PAN), poly(methyl methacrylate) (PMMA), poly(vinylidene fluoride (PVdF), polyvinyl chloride (PVC) or a derivative thereof.
  • the voltage cycling boundary limits of the battery have to be from about 2 to 3V vs. Li + /Li for the lower limit and from about 4.6 to 4.8 V vs. Li + /Li for the upper limit.
  • the mean operating voltage is generally about 3.4 to 3.8 V vs. Li + /Li on discharge.
  • Example n o 1 the 0.75Li 2 MnO 3 .0.25LiNi 0.6 Mn 0.2 Mg 0.2 O 2 compound was synthesized and then tested in a lithium battery of “buttoncell” format.
  • the 0.75Li 2 MnO 3 .0.25LiNi 0.6 Mn 0.2 Mg 0.2 O 2 compound is in particular obtained by intimately mixing 2 g of a previously synthesized precursor A and 1.502 g of lithium hydroxide LiON.H 2 O, by heating the mixture at 900° C. for 24 hours and then cooling it very quickly to ambient temperature (quenching).
  • the precursor A was previously synthesized from:
  • Characterization of the product obtained after the quenching operation confirms synthesis of the 0.75Li 2 MnO 3 .0.25LiNi .,6 Mn .,2 Mg 0.2 O 2 compound and its lamellar-type structure.
  • a “buttoncell” format lithium battery is then achieved with:
  • FIG. 1 The variation of the specific capacity versus the number of cycles corresponding to this lithium battery is represented by plot A in FIG. 1 .
  • FIG. 1 also comprises plots B and C corresponding to the variation of the specific capacity versus the number of cycles for two similar batteries but respectively implementing 0.7Li 2 MnO 3 .0.3LiMn 1/3 Ni 1/3 Co 1/3 O 2 and 0.75Li 2 MnO 3 .0.25LiNiO 2 as active positive electrode material.
  • Plot A enables it to be observed that the specific capacity obtained with the 0.75Li 2 MnO 3 .0.25LiNi 0.6 Mn 0.2 Mg 0.2 O 2 oxide is relatively constant whatever the number of cycles.
  • Example n o 2 the 0.75Li 2 MnO 3 .0.25LiNi 0.9 Mn 0.05 Mg 0.05 O 2 compound was synthesized and then tested in a “buttoncell” format lithium battery similar to the one produced in example n o 1.
  • the 0.75Li 2 MnO 3 .0.25LiNi 0.9 Mn 0.05 Mg 0.05 O 2 compound is in particular synthesized by intimately mixing 1.50 g of a previously synthesized precursor A′ and 1.11 g of lithium hydroxide LiOH.H 2 O, and by then heating the mixture at 1000° C. for 24 hours before cooling it very quickly to ambient temperature (quenching).
  • precursor A′ was previously synthesized from:
  • Precursor A′ is represented by the general formula Mn 0.7625 Ni 0.225 Mg 0.0125 (OH) 2 .
  • the 0.75Li 2 MnO 3 .0.25LiNi 0.9 Mn 0.05 Mg 0.055 O 2 compound thus synthesized was characterized by X-ray diffraction ( FIG. 2 ) and by scanning electron microscopy observation ( FIG. 3 ).
  • FIG. 2 enables the composition of the synthesized compound to be confirmed and
  • FIG. 3 confirms the lamellar-type structure of the compound.
  • Such a compound was further used as active material of a positive electrode in a “buttoncell” format lithium battery similar to the battery produced in example n o 1. Only the active material of the positive electrode was replaced in the lithium battery according to example n o 1.
  • FIGS. 4 and 5 illustrate the electrochemical characteristics corresponding to this lithium battery. It can thus be observed in FIG. 4 that the specific capacity of the lithium battery is stable on cycling.
  • the value of the specific capacity (plot D) is in fact substantially constant whatever the number of cycles applied.
  • the mean loss of capacity per cycle is in fact estimated, over the first 80 cycles, at only 0.01%. For comparison purposes, this loss is generally about 0.04% for a commercial Lithium battery.
  • FIG. 4 comprises an insert representing the first discharge (plot E) of the battery, performed in intentiostatic mode, under C/10 conditions at a temperature of 55° C., for potentials varying between 3 and 4.8V vs Li + /Li.
  • Plot E thus corresponds to the variation of the potential with respect to the potential of the Li + /Li pair, versus the specific capacity.
  • the specific capacity of the battery is 200 mAh/g at the first discharge.
  • Plot F of FIG. 5 indicates that it is moreover possible to obtain, in the case of the 0.75Li 2 MnO 3 .0.25LiNi 0.9 Mn 0.05 Mg 0.05 O 2 compound and after 100 charging/discharging cycles:
  • the mass energy is very high in comparison with that obtained with active materials used in currently marketed batteries (generally about 600 Wh/kg), all the more so as it is obtained after a large number of cycles.
  • 0.75Li 2 MnO 3 .0.25LiNi 0.6 Mn 0.2 Mg 0.2 O 2 and 0.75Li 2 MnO 3 .0.25LiNi 0.9 Mn 0.05 Mg 0.05 O 2 oxides and more generally the oxide family of xLi 2 MnO 3 .(1 ⁇ x)LiM 1 a M 2 b M 3 c O 2 , type enable high capacities to be attained, while at the same time maintaining a good stability over a large number of charging/discharging cycles. In certain cases, it is possible to obtain specific capacity values or more than 300 mAh/g, which represents an increase of 100% compared with the active materials for the positive electrode used in lithium batteries, such as the LiCoO 2 oxide.
  • the oxides according to the invention are advantageously prepared by thermally treating a powder obtained by mixing a precursor forming a source of elements M 1 , M 2 and M 3 in predetermined proportions with lithium hydroxide LiOH.H 2 O, at a temperature at least equal to 800° C. and more often of about 900° C. to 1000° C.
  • the precursor is in particular represented by the general formula Mn x M 1 a(1-x) M 2 b(1-x) M 3 c(1-x) (OH) 2 .
  • the oxide can be subjected to post-treatment in a slightly acid aqueous solution to improve its electrochemical properties and therefore the specific capacity of the lithium battery.
  • Example n o 3 10 g of the 0.75Li 2 MnO 3 .0.25LiNi 0.9 Mn 0.05 Mg 0.05 O 2 compound obtained according to example n o 2 are mixed with 250 mL of an aqueous solution having a pH equal to 5.5.
  • the aqueous solution is for example water in which an acid such as H 2 SO 4 or HNO 3 is added to adjust the pH.
  • the mixture is then stirred for 30 minutes, and is then placed in an ultrasonic tank for 10 minutes.
  • the mixture finally placed under magnetic stirring for 24 hours.
  • a centrifugation operation consisting in three washings with water enables a powder to be recovered, which powder is then dried at 50° C. for 24 hours. Finally the powder is subjected to heat treatment at a temperature of 350° C., for 3 hours in air.
  • the compound treated in this way is then tested as active material for the positive electrode in a “buttoncell” format battery respectively with cycling temperatures at 20° C. and at 55° C.
  • the battery is similar to the batteries produced according to examples n o 1 and 2. It thus comprises the same constituents as the batteries produced according to examples n o 1 and 2, with the exception of the active material of the positive electrode.
  • the specific capacity is equal to 317 mAh/g for a cycling temperature of 55° C. (plot G) and it is 252 mAh/g for a cycling temperature of 20° C. (plot H).
  • the specific capacity obtained for a cycling temperature of 20° C. with active materials for the positive electrode according to the prior art is lower. For example it is about 150 mAh/g, at 20° C., for compounds of xLi 2 MnO 3 .(1 ⁇ x)LiMO 2 type.
  • the mean potential on discharge is 3.656 V vs. Li + /Li at 20° C. (i.e.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
US12/996,510 2008-06-05 2009-05-28 Positive electrode material formed by a lamellar-type oxide for a lithium battery Active 2029-12-07 US8323532B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0803139 2008-06-05
FR0803139A FR2932175B1 (fr) 2008-06-05 2008-06-05 Materiau d'electrode positive forme d'un oxyde de type lamellaire pour accumulateur au lithium.
PCT/FR2009/000625 WO2009147315A1 (fr) 2008-06-05 2009-05-28 Matériau d'électrode positive formé d'un oxyde de type lamellaire pour accumulateur au lithium.

Publications (2)

Publication Number Publication Date
US20110089369A1 US20110089369A1 (en) 2011-04-21
US8323532B2 true US8323532B2 (en) 2012-12-04

Family

ID=40386430

Family Applications (1)

Application Number Title Priority Date Filing Date
US12/996,510 Active 2029-12-07 US8323532B2 (en) 2008-06-05 2009-05-28 Positive electrode material formed by a lamellar-type oxide for a lithium battery

Country Status (11)

Country Link
US (1) US8323532B2 (de)
EP (1) EP2318315B1 (de)
JP (1) JP5512662B2 (de)
KR (1) KR20110031420A (de)
CN (1) CN102056844B (de)
AT (1) ATE533732T1 (de)
BR (1) BRPI0913629A2 (de)
ES (1) ES2377602T3 (de)
FR (1) FR2932175B1 (de)
PL (1) PL2318315T3 (de)
WO (1) WO2009147315A1 (de)

Families Citing this family (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5605641B2 (ja) * 2010-12-16 2014-10-15 トヨタ自動車株式会社 リチウム二次電池
FR2970376B1 (fr) * 2011-01-07 2013-01-25 Commissariat Energie Atomique Materiau d'electrode positive biphase pour accumulateur au lithium et son procede de synthese
JP5586532B2 (ja) 2011-06-23 2014-09-10 株式会社東芝 非水電解質電池及び電池パック
JP5686378B2 (ja) * 2011-12-07 2015-03-18 株式会社豊田自動織機 水素含有リチウムシリケート系化合物及びその製造方法、並びに非水電解質二次電池用正極活物質、非水電解質二次電池用正極、非水電解質二次電池及び車両
CN102522590B (zh) * 2011-12-26 2014-09-17 华为技术有限公司 一种非水有机电解液、包含它的锂离子二次电池及其制备方法和终端通讯设备
AU2014248900C1 (en) 2013-03-12 2017-06-08 Apple Inc. High voltage, high volumetric energy density Li-ion battery using advanced cathode materials
CN106233513B (zh) * 2014-03-12 2019-08-06 株式会社Lg 化学 正极活性材料和包含它的锂二次电池
US9716265B2 (en) 2014-08-01 2017-07-25 Apple Inc. High-density precursor for manufacture of composite metal oxide cathodes for Li-ion batteries
EP3220393B1 (de) * 2014-11-10 2021-06-30 Murata Manufacturing Co., Ltd. Glaskeramik, lithium-ionen-leiter, zelle, elektronische vorrichtung und verfahren zur herstellung der elektrode
JP6422742B2 (ja) * 2014-11-11 2018-11-14 日立オートモティブシステムズ株式会社 リチウムイオン二次電池および電池システム
KR101669241B1 (ko) 2015-01-29 2016-10-25 주식회사 케이알 손잡이를 갖는 퍼프
JPWO2016140352A1 (ja) * 2015-03-04 2018-01-18 日揮触媒化成株式会社 非水電解質二次電池用正極活物質、正極及び非水電解質二次電池
CN105576202B (zh) * 2015-12-21 2018-03-06 哈尔滨工业大学 一种富锂锰硒基正极材料及其制备方法
KR102473532B1 (ko) * 2015-12-31 2022-12-05 삼성전자주식회사 양극 활물질 및 상기 양극 활물질을 채용한 양극과 리튬 전지
US20170214045A1 (en) * 2016-01-22 2017-07-27 Apple Inc. High-energy cathode active materials for lithium-ion batteries
US11362331B2 (en) 2016-03-14 2022-06-14 Apple Inc. Cathode active materials for lithium-ion batteries
EP3281915B1 (de) * 2016-08-10 2019-02-20 Umicore Vorläufer für lithium-übergangsmetalloxid-kathodenmaterial für wiederaufladbare batterien
CN109715561B (zh) 2016-09-20 2020-09-22 苹果公司 具有改善的颗粒形态的阴极活性材料
WO2018057621A1 (en) 2016-09-21 2018-03-29 Apple Inc. Surface stabilized cathode material for lithium ion batteries and synthesizing method of the same
CN110707298B (zh) * 2018-07-10 2021-11-12 比亚迪股份有限公司 正极材料及其制备方法、锂离子电池和车辆
CN110707297B (zh) * 2018-07-10 2021-05-14 比亚迪股份有限公司 正极材料及其制备方法、锂离子电池和车辆
US11695108B2 (en) 2018-08-02 2023-07-04 Apple Inc. Oxide mixture and complex oxide coatings for cathode materials
US11749799B2 (en) 2018-08-17 2023-09-05 Apple Inc. Coatings for cathode active materials
CN109119628B (zh) * 2018-08-21 2021-07-30 中南大学 一种共掺杂改性的高镍三元材料及制备方法
US11757096B2 (en) 2019-08-21 2023-09-12 Apple Inc. Aluminum-doped lithium cobalt manganese oxide batteries
EP3800708A1 (de) * 2019-10-01 2021-04-07 Centre National de la Recherche Scientifique Verwendung einer übergangsmetallsulfidverbindung in einer positiven elektrode für festkörperbatterien
US20210119208A1 (en) * 2019-10-18 2021-04-22 Ecopro Bm Co., Ltd. Positive electrode active material for lithium secondary battery, method for preparing the same, and lithium secondary battery including the same
CN114556628A (zh) * 2019-10-18 2022-05-27 Ecopro Bm有限公司 锂二次电池正极活性物质、其制备方法以及包含其的锂二次电池
CN113422039A (zh) * 2021-06-24 2021-09-21 北京车和家信息技术有限公司 三元系复合氧化物基体材料、三元正极材料及制备方法与由其制备的锂离子电池

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5443929A (en) * 1992-09-25 1995-08-22 Sanyo Electric Co., Ltd. Nonaqueous secondary battery
US6677082B2 (en) * 2000-06-22 2004-01-13 The University Of Chicago Lithium metal oxide electrodes for lithium cells and batteries
US6680143B2 (en) * 2000-06-22 2004-01-20 The University Of Chicago Lithium metal oxide electrodes for lithium cells and batteries
WO2004107480A2 (en) 2003-05-28 2004-12-09 National Research Council Of Canada Lithium metal oxide electrodes for lithium cells and batteries
US20050136329A1 (en) 2003-12-23 2005-06-23 Howard Wilmont F.Jr. High voltage laminar cathode materials for lithium rechargeable batteries, and process for making the same
EP1837937A1 (de) 2006-03-20 2007-09-26 National Institute of Advanced Industrial Science and Technology Mischoxid auf der Basis von Lithium und Mangan sowie Herstellungsverfahren dafür
WO2008086041A1 (en) 2007-01-10 2008-07-17 Nanoexa, Inc. Lithium batteries with nano-composite positive electrode material

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3539518B2 (ja) * 1995-08-11 2004-07-07 日立マクセル株式会社 リチウム二次電池
KR100895354B1 (ko) * 2004-09-03 2009-04-29 유시카고 아곤, 엘엘씨 리튬 배터리를 위한 망간 옥사이드 복합 전극
KR101264332B1 (ko) * 2006-09-20 2013-05-14 삼성에스디아이 주식회사 캐소드 활물질 및 이를 채용한 리튬 전지
JP5484771B2 (ja) * 2008-09-26 2014-05-07 日産自動車株式会社 リチウムイオン電池用正極
JP5392813B2 (ja) * 2008-10-31 2014-01-22 日産自動車株式会社 リチウムイオン電池とその使用方法
JP5272870B2 (ja) * 2009-04-17 2013-08-28 株式会社Ｇｓユアサ リチウム二次電池用活物質、リチウム二次電池用電極及びリチウム二次電池

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5443929A (en) * 1992-09-25 1995-08-22 Sanyo Electric Co., Ltd. Nonaqueous secondary battery
US6677082B2 (en) * 2000-06-22 2004-01-13 The University Of Chicago Lithium metal oxide electrodes for lithium cells and batteries
US6680143B2 (en) * 2000-06-22 2004-01-20 The University Of Chicago Lithium metal oxide electrodes for lithium cells and batteries
WO2004107480A2 (en) 2003-05-28 2004-12-09 National Research Council Of Canada Lithium metal oxide electrodes for lithium cells and batteries
US20050136329A1 (en) 2003-12-23 2005-06-23 Howard Wilmont F.Jr. High voltage laminar cathode materials for lithium rechargeable batteries, and process for making the same
EP1837937A1 (de) 2006-03-20 2007-09-26 National Institute of Advanced Industrial Science and Technology Mischoxid auf der Basis von Lithium und Mangan sowie Herstellungsverfahren dafür
WO2008086041A1 (en) 2007-01-10 2008-07-17 Nanoexa, Inc. Lithium batteries with nano-composite positive electrode material

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
International Search Report issued in International Application No. PCT/FR2009/000625, mailed on Oct. 16, 2009. (with English-language translation).
Johnson et al., "Lithium-manganese oxide elctrodes with layered-spinel composite structures xLi2MnO3 . (1-x)Li1+yMn2-yO4 (0<x<1, 0≰y≰0.33) for lithium batteries," Electrochemistry Communications 7, 2005, pp. 528-536.
Johnson et al., "Lithium-manganese oxide elctrodes with layered-spinel composite structures xLi2MnO3 • (1-x)Li1+yMn2-yO4 (0<x<1, 0≦y≦0.33) for lithium batteries," Electrochemistry Communications 7, 2005, pp. 528-536.
Kim et al., "Electrochemical and Structural Properties of xLi2M′O3•(1-x)LiMn0.5Ni0.5O2 Electrodes for Lithium Batteries (M′=Ti, Mn, Zr; 0≦x≦0.3)," Chem. Mater. 2004, 16, pp. 1996-2006.
Kim et al., "Electrochemical and Structural Properties of xLi2M'O3.(1-x)LiMn0.5Ni0.5O2 Electrodes for Lithium Batteries (M'=Ti, Mn, Zr; 0≰x≰0.3)," Chem. Mater. 2004, 16, pp. 1996-2006.
Thackeray et al., "Advances in manganese-oxide 'composite' electrodes for lithium-ion batteries," Journal of Materials Chemistry, 15, 2005, pp. 2257-2267.
Thackeray et al., "Comments on the structural complexity of lithium-rich Li1+xM1-xO2 electrodes (M=Mn, Ni, Co) for Lithium batteries," Electrochemistry Communications 8, 2006, pp. 1531-1538.

Also Published As

Publication number Publication date
BRPI0913629A2 (pt) 2015-11-24
JP2011522383A (ja) 2011-07-28
CN102056844A (zh) 2011-05-11
EP2318315A1 (de) 2011-05-11
FR2932175B1 (fr) 2011-06-03
ATE533732T1 (de) 2011-12-15
EP2318315B1 (de) 2011-11-16
PL2318315T3 (pl) 2012-04-30
KR20110031420A (ko) 2011-03-28
FR2932175A1 (fr) 2009-12-11
WO2009147315A1 (fr) 2009-12-10
CN102056844B (zh) 2013-09-04
ES2377602T3 (es) 2012-03-29
JP5512662B2 (ja) 2014-06-04
US20110089369A1 (en) 2011-04-21

Similar Documents

Publication Publication Date Title
US8323532B2 (en) Positive electrode material formed by a lamellar-type oxide for a lithium battery
JP4197237B2 (ja) 正極活物質の製造方法
EP1909345B1 (de) Aktives Kathodenmaterial für eine Lithiumbatterie
US7927506B2 (en) Cathode active material and lithium battery using the same
US7309546B2 (en) Positive active material for rechargeable lithium battery
US9112237B2 (en) Electrolyte for rechargeable lithium battery and rechargeable lithium battery including same
US8999579B2 (en) Surface treated anode active material and method of making the same, anode including the same, and lithium battery including the same
JP4968578B2 (ja) 正極活物質、その製造方法および非水電解質二次電池
US20070292760A1 (en) Lithium-ion storage battery comprising TiO2-B as negative electrode active material
JP5308675B2 (ja) 電池に最適な陽極物質、その製造方法、電極、及び該方法を実施するためのバッテリー
KR20160074236A (ko) 복합 양극 활물질, 그 제조방법, 이를 포함한 양극 및 리튬 전지
JP2007194202A (ja) リチウムイオン二次電池
KR102220490B1 (ko) 리튬 이차 전지용 양극 활물질, 이의 제조방법 및 이를 포함하는 리튬 이차 전지
US10170762B2 (en) Lithium metal oxides with multiple phases and stable high energy electrochemical cycling
JP2021501978A (ja) リチウム二次電池用非水電解液およびそれを含むリチウム二次電池
JP2008293997A (ja) 正極活物質および非水電解質二次電池
KR20200022359A (ko) 양극 활물질, 이의 제조 방법 및 이를 포함하는 양극과 리튬 이차 전지
CN103210532B (zh) 二次电池用正极活性物质和使用其的二次电池
JP2004055247A (ja) 二次電池および二次電池用集電体
KR101754612B1 (ko) 리튬 이차 전지용 양극 및 이를 포함하는 리튬 이차 전지
KR101224618B1 (ko) 리튬 이차전지용 양극 활물질, 리튬 이차전지용 양극, 리튬 이차전지 및 이들의 제조방법
JP2008071622A (ja) 非水電解質二次電池用正極活物質およびその製造方法
JPH10241685A (ja) 非水電解質二次電池
US20220278358A1 (en) Manufacturing method of lithium secondary battery
US8338031B2 (en) Cathode and lithium battery including the same

Legal Events

Date Code Title Description
AS Assignment

Owner name: COMMISSARIAT A L'ENERGIE ATOMIQUE ET AUX ENERGIES

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:PATOUX, SEBASTIEN;BOURBON, CAROLE;REEL/FRAME:025593/0202

Effective date: 20101119

STCF Information on status: patent grant

Free format text: PATENTED CASE

FPAY Fee payment

Year of fee payment: 4

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 8TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1552); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 8

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 12TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1553); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 12